Herbicide

ABSTRACT

New and valuable herbicide comprising several herbicidal active ingredients.

United States Patent [1 Fischer 1 HERBICIDE [75] Inventor: Adolf Fischer, Mutterstadt, Germany [73] Assignee: Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen, Rhine, Germany [22] Filed: Apr. 4, 1973 [21] Appl. No.: 348,084

[52] US. Cl 7l/92, 71/100, 71/111 [51] Int. Cl A0ln 9/22 [58] Field of Search 71/100, 92, 111

[ Mar. 11, 1975 Primary E.\'aminer.lames 0. Thomas, Jr. Attorney, Agent, or Firm-Johnson, Keil, Thompson & Shurtleff [57] ABSTRACT New and valuable herbicide comprising several herbicidal active ingredients.

5 Claims, N0 Drawings 1' 2 HERBICIDE or NH-COCOOR, R denoting tert-butyl or isopropyl, has a good herbicidal action.

The present invention relates to a herbicide compris- Th active i di may be used in any weight ing a mixture of a thiol carbamate and a biscarbamate, I i but it i p f d to employ a ratio of 1, d uracil or Pyndazoneof from 1:5 to 5:1, particularly from 1:3 to 3:1.

It is known to use thiol carbamates, biscarbamates, The agents according to the invention may be used wells and pyndazones for colmoumg as herbicides in the form of solutions, emulsions, susand grassy weeds. However, their herbicidal action 18 p pensions, Oll dispersions, granules or dusts. The form of I h'ave now found that a composition of 1 application depends entirely on the purpose for which a. a thio] carbamate of the formula the agents are being used; in any case it should ensure a time distribution of the active ingredient.

For the preparation of solutions to be sprayed direct,

R 5 mineral Oll fractions of medium to high boiling pomt, -fisuch as kerosene or diesel oil, further coal-tar oils and R O OllS of vegetable or mineral origin, and cyclic hydrocarbons such as tetrahydronaphthalene and alkylated where R denotes lower alkyl or alkynyl or a maximum naphthalenes are suitable. f 4 carbon atoms, R2 denotes cyclohexyl or a y- Aqueous formulations may be prepared from emul- Cloaliphatic Ol' tricycloaliphatic hydrocarbon radical Of Sign concentrates pastes or wettable powders add- 3 a maxlmum of 8 carbon atoms and R denotes lower mg water. To prepare emulsions the ingredients as such alkyl of a maximum of 4 Carbon atoms and or dissolved in a solvent may be homogenized in water a Compound of the formula or organic solvents by means of wetting or dispersing agents, e.g., polyethylene oxide adducts. Concentrates which are suitable for dilution with water may be pre- @NH9- pared from active ingredient, wetting agent, adherent,

X 0 emulsifying or dispersing agent and possibly solvent.

NHCOOCH; Oils-of various types may be added to ready-to-use 3O spray liquors. where X denote meth l, Dusts may be prepared by mixing or grinding the acc. a compound of the formula tive ingredients with a solid carrier, e.g., clay or fertilizers.

Granules may be prepared by bonding the active in- O gredients to solid carriers.

Directly sprayable dispersions may also be prepared ,g with oils. The new compounds may be mixed with fertilizers, insecticides, fungicides and other herbicides.

EXAMPLE 1 where R denotes y g or the radical I The seeds of beet (Beta vulgaris), wild mustard (Sinapis arvensis), common lambsquarters (Chenopodium album), perennial ryegrass (Lolium perenne), downy brome (Bromus tectorum) and barnyard grass 5 (Echnichloa crus-galli) were sown on an agricultural 'E'Q' Q E 3 or plot. The soil prepared in this manner was subsequently 0 CH 0 treated with the following amounts of the following active ingredients and compositions thereof, each active d. a compound of the formula ingredient and each composition being dispersed or emulsified in 500 liters of water per hectare:

l ethyl-N-ethyl-N-bicyclo-[2,2,1]-heptylthiol car- X bamate, 1.5 and 2 kg/hectare; 6f ll thioethyl N-cyclohexyl-N-propargyl carbamate, 2

and 3 kg/hectare; TI 0 111 l- (a,a-dimethyl-B-acetoxypropionyl)-3 (j cyclohexyl-S,6-trimethylene uracil, 0.5 and 2 l kg/hectare;

IV 3-cyclohexyl-5,o-trimethylene uracil, l and 3 kg/hectare;

l+ lIl 1.5 0.5 kg/hectare; ll IV 2 l kg/hectare. The following figures show that the compositions OH have a better herbicidal action than their individual I components, combined with the same good crop plant compatibility:

where Y denotes chlorine or bromine and X denotes album I ll [ll L5 2 2 3 0.5 2

Beta vulgaris 0 0 0 0 20 Sinapis arvensis 15 20 l0 I5 55 I00 Chenopodium 2s 35 40 15 45 100 5 album Lolium perenne 60 70 55 75 30 95 Bromus tectorum 45 55 50 70 25 90 Echinochloa 60 75 60 85 30 85 crus-galli W r+m MW 1 3 1.5 0.5 2+1 Beta vulgaris 0 45 0 0 Sinapis arvensis 60 I00 I00 95 Chenopodium album 55 I00 100 100 Lolium perenne 35 100 100 I00 Bromus tectorum 35 100 95 100 Echinochloa crus-gulli 35 I00 l00 100 0 da c 100 destruction EXAMPLE 2 In the greenhouse, loamy sandy soil was filled into pots and sown with beet (Beta vulgaris), lndian com (Zea mays), wild mustard (Sinapis arvensis), common lambsquarters (Chenoopodium album), barnyard grass (Echinochloa crus-galli), perennial ryegrass (Lolium perenne) and downy brome (Bromus tectorum).

The soil was then treated with the following amounts of the following active ingredients and compositions thereof, each active ingredient and each composition being emulsified or dispersed in 500 liters of water per hectare:

1 ethyl-N-ethyl-N-bicyclo-[2,2,l ]-heptylthiol carbamate, 1.5 and 3 kg/hectare;

ll ethyl N-ethyl-N-cyclohexylthiol carbamate, 1.5

and 4 kg/hectare;

lll 1-phenyl-4-(a-hydroxy-B,B,B-trichloroethyl)- amino-5-bromopyridazone-(6), 1.5 and 3 kg/hectare;

IV isopropyl N-[1-phenyl-5-bromopyridazon-(6)-yl- (4)]-oxamate, 2.5 and 4 kg/hectare;

l+ lll 1.5 l.5 kg/hectare;

ll W 1.5 2.5 kg/hectare.

The results given below show that the compositions have a better overall herbicidal action than their individual components, combined with excellent crop plant Active 1 ll lll ingredient kg/ha Echinochloa crus-galli Lolium perenne Bromus tectorum Active ingredient kg/ha Beta vulgaris Zea mays Sinapis arvensis Chenopodium album Echinochloa crus-galli Lolium perenne Bromus tectorum 0 no damage 100 complete destruction EXAMPLE 3 In the greenhouse, the plants beet (Beta vulgaris), Indian corn (Zea mays), wild mustard (Sinapis arvensis), common lambsquarters (Chenopodium album), chamomile (Matricaria chamomilla), downy brome (Bromus tectorum) and slender foxtail (Alopecurus myosuroides) were treated at a growth height of 4 to 18 cm with the following amounts of the following active ingredients and compositions thereof, each active ingredient and each composition being emulsified in 500 liters of water per hectare:

- 5O patibility:

compatibility:

Active ingredient I ll lll kg/ha I 2 3 l 3 l 2 Beta vulgar-is 0 0 10 o 30 0 20 Zea mays 0 0 0 0 20 0 20 Sinapis arvensis 5 10 20 85 l00 75 100 Chenopodium album 5 I0 20 85 l00 70 100 Matricaria chamomilla I0 20 35 40 95 70 I00 Bromus tectorum 30 85 5 10 30 Alopecurus myosuroides 30 65 90 l0 20 35 90 Active ingredient lV l+|l l+lll l+lV kg/ha 2 3 2+l l+l 1+2 Beta vulgaris 0 20 0 0 0 Zea mays 5 20 0 0 5 Sinapis arvensis 70 I00 I00 95 95 Chenopodium album 100 I00 95 100 Matricaria chamomilla 70 I00 I00 95 95 Bromus tectorum 40 70 95 Alopecurus myosuroides 40 70 95 90 95 0 no damage I00 complete destruction The action of the following compositions corresponds to that of those described in Example 1:

thioethyl N-bicyclo-(3,3,0)-octyl-N-propyn-(2)-yll )-carbamate l-(a,a,-dimethyl-,8- acetoxypropionyl)-3-cyclohexyl-5,o-trimethylene uracil ethyl-N-ethyl-N-bicyclo-[2,2,l l-hepthylthiol bamate 3-cyclohexyl-5,6-trimethyl uracil thioethyl N-bicyclo-(3,3,0)-octyl-N-propyn-(2)-yll )-carbamate l-(a,a-dimethyl-,B- acetoxypropionyl)-3-cyclohexyl-5,6-trimethylene uracil ethyl-N-ethyl-N-bicyclo-[2,2,l ]-hepthylthiol car- The results are given below:

Active ingredient I ll lll l+ ll l lll kg/ha 1.5 1.75 2 0.5 1.75 0.5 2 l 5 +0.25 1.5 0.5

Beta vulgaris 0 0 0 0 l5 0 30 0 0 Bromus tectorum 40 50 55 25 70 25 75 85 95 Chenopodium album I0 20 25 45 8O 35 65 85 85 Echinochloa crus-galli 60 65 65 30 65 25 75 100 I00 Sinapis arvensis l0 55 80 40 70 85 90 0 no damage I00 complete destruction bamate l-(a,a-dimethyl-B-acetoxypropionyl)-3- lclaim:

cyclohexyl-S,6-trimethylene uracil N-lor 2- 1. A selective herbicide composition containing a bicyclo-(3,3,0)-octyl-N-ethylethylthiol carbamate l-(a,a-dimethyl-B-acetoxypropionyl )-3- cyclohexyl-S,6-trimethylene uracil N- l or 2-bicyclo-(3,3,0)-octyl-N-ethylethylthiol carbamate 3-cyclohexyl-5,6-trimethylene uracil methyl N-lor 2-bicyclo-(3,3,0)-octyl-N-ethylthiocarbamate l-(a,a-dimethyl-B- acetoxypropionyl)-3-cyclohexyl-5,6- trimethyleneuracil.

The action of the following compositions corresponds to that of those described in Example 2:

ethyl-N-ethyl-N-bicyclo-[2,2,ll-heptylthiol carbamate tert-butyl N-[1-phenyl-5-bromopyridazon- (6)-yl-(4)]-oxamate, ethyl N-lor 2-bicyclo- (3,3,0J-octyl-N-ethylthiocarbamate, l-phenyl-4- (a-hydroxy-B,,B,l3-trichloroethyl)-amino-5- bromopyridazone-(), ethyl. N-lor 2-bicyclo- (3,3,0)-octyl-N-ethylthiocarbamate, isopropyl N- [l-phenyl-5-bromopyridazorr(6)-yl;4)j-oxamate,

" ethyl-N ethyI N-bicyclo-[2,2,1]-heptylthiol carbamate l-phenyl-4-(a-hydroxy-B,B,B- trichloroethylamino-5-chloropyridazone-(6) thioethyl N-[lor 2-(3a,4,5,6,7,7a-hexahydro-4,7- methanoindanyl)l-N-ethylcarbamate l-phenyl- 4-(a-hydroxy-B,B,B-trichloroethyl) amino-5- bromopyridazone-(6) ethyl N-lor 2-bicyclo-(3,3,0)-octyl-N-ethylthiocarbamate l-phenyl-4-(a-hydroxy-,B,/3,,B- trichloroethyl )-amino-5-bromopyridazone-( 6), thioethyl N-bicyclooctyl-(3,2,l )-N-propyn-(2)-yll )carbamate, l-phenyl-4-(a-hydroxy-B,B,fltrichloroethyU-amino-5-bromopyridazone-(6).

EXAMPLE 4 In the greenhouse, loamy sandy soil was filled into pots and sown with seeds of the plants listed below. The soil was then treated with the following amounts of the following active ingredients and compositions thereof, each active ingredient and each composition being emulsified in 500 liters of water per hectare:

herbicidally effective amount of a. a thiol carbamate of the formula wherein R denotes lower alkyl or alkynyl of a maximum of 4 carbon atoms, R denotes cyclohexyl or a bicycloaliphatic or tricycloaliphatic hydrocarbon radical of a maximum of 8 carbon atoms and R denotes lower alkyl of a maximum of 4 carbon atoms and b. a compound of the formula where Y denotes chlorine or bromine and X denotes -NH-CH-CC1 or NHCOCOO-R, R denoting tert-butyl or isopropyl, in a weight ratio of a to b in the range of 1:5 to

7 (3,3,0)-octyl-N-ethylethylthiol carbamate, methyl N-lor 2-bicyclo-(3,3,0)-octyl-N-ethylthiocarbamate, ethyl N-lor 2-bicyclo-(3,3,0)-octyl-N-ethylthiocarbamate, thioethyl N-[ lbicyclo-(3,3,0)-octyl-N-methylthiocarbamate, and thioethyl N-bicyclooctyl-(3,2,l )-N-propyn-(2)-yl-( l carbamate.

4. A selective herbicide composition as claimed in claim 2 wherein compound b is selected from the group consisting of l phenylA-(g hydroggyflii,p-

t richloroe thyl) Imino-5-brdmopyridazone-(6), isoproor 2-(3a,4,5,6,7,7a-hexahydro-4,7-- methanoindanyl)J-N-ethylcarbamate, ethyl N-lor 2- UNITED STATES PATENT AND TRADEMARK OFFICE I CERTIFICATE OF CORRECTION PATENT No. 3,870,502 I DATED March 11, 197.5

INVENTOR( I Adolf Fischer It is certified that error appears in the above-identified patent and that said Letters Patent 7 are hereby corrected as shown below:

a In the Heading, insert --[30] Foreign Application Priority Data April 15, 1972 Germany P 2.2 18 347.7"

In Column 5, Line 8, delete -5, 6-trimethyl uracil" and substitute -5,6-trimethylene uracil In Column 6, Lines 6 6; 7 of Claim 3, delete "cyclohexylthiol carbamate, 3-methoxycarbonylaminophenyl-N-thioethyl N-bicyclo" and substitute --cyclohexylthiol carbamate, thioethyl N-bicyclo-(3,3,0)-0ctyl-N-pr0pyn-(2)-yl-(l)-carbamate-- E Signed and Scaled this Seventeenth Day August 1976 [SEAL] Arrest:

RUTH cMAsoN c. MARSHALL DANN Arresting Office Commissioner of Patents and Trademarks 

1. A SELECTIVE HERBICIDE COMPOSITION CONTAINING A HERBICIALLY EFFECTIVE AMOUNT OF A. A THIOL CARBAMATE OF THE FORMULA
 1. A selective herbicide composition containing a herbicidally effective amount of a. a thiol carbamate of the formula
 2. A selective herbicide composition as claimed in claim 1 wherein said weight ratio is 1:3 to 3:1.
 3. A selective herbicide composition as claimed in claim 1 wherein compound a is a member selected from the group consisting of ethyl-N-ethyl-N-bicyclo(2,2,1)-heptylthiol carbamate, thioethyl N-cyclohexyl-N-propargyl carbamate, ethyl N-ethyl-N-cyclohexylthiol carbamate, thioethyl N-bicyclo-(3,3,0)-octyl-N-propyn-(2)-yl-(1)carbamate, N-1- or 2-bicyclo-(3,3,0)-octyl-N-ethylethylthiol carbamate, methyl N-1- or 2-bicyclo-(3,3,0)-octyl-N-ethylthiocarbamate, ethyl N-1- or 2-bicyclo-(3,3,0)-octyl-N-ethylthiocarbamate, thioethyl N-(1- or 2-(3a,4,5,6,7,7a-hexahydro-4,7-methanoindanyl))-N-ethylcarbamate, ethyl N-1- or 2-bicyclo-(3,3,0)-octyl-N-methylthiocarbamate, and thioethyl N-bicyclooctyl-(3,2,1)-N-propyn-(2)-yl-(1)-carbamate.
 4. A selective herbicide composition as claimed in claim 2 wherein compound b is selected from the group consisting of 1-phenyl-4-( Alpha -hydroxy- Beta , Beta , Beta -trichloroethyl)-amino-5-bromopyridazone-(6), isopropyl N-(1-phenyl-5-bromopyridazon-(6)-yl-(4))-oxamate, isopropyltert-butyl N-(1-phenyl-5-bromopyridazon-(6)-yl-(4))-oxamate, and 1-phenyl-4-( Alpha -hydroxy- Beta , Beta , Beta -trichloroethyl)-amino-5-chloropyridazone-(6). 